CN103910437A - Method for removing heavy metal ions out of water - Google Patents
Method for removing heavy metal ions out of water Download PDFInfo
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- CN103910437A CN103910437A CN201410158294.0A CN201410158294A CN103910437A CN 103910437 A CN103910437 A CN 103910437A CN 201410158294 A CN201410158294 A CN 201410158294A CN 103910437 A CN103910437 A CN 103910437A
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Abstract
The invention belongs to the field of the environmental pollution control method and specifically relates to a method for removing heavy metal ions out of water. The method comprises the steps of mixing penicillium simplicissimum spores and a heavy metal ion solution to obtain a mixed solution, next, adding charcoal dust to the mixed solution, and then carrying out culturing and separation processes, thus completing the adsorption and removal of heavy metal ions out of the water. The method is characterized in that an immobilized object and an immobilization carrier are exchanged, the penicillium simplicissimum mycelia are taken as the carrier to immobilize the charcoal dust, the reducing adsorption action of the charcoal and the penicillium simplicissimum on hexavalent chromium (Cr<6+>) in water and the adsorption effect of the charcoal and the penicillium simplicissimum on heavy metal ions such as cadmium (Cd<2+>), lead (Pb<2+>) and copper (Cu<2+>) in water are achieved simultaneously, and therefore, charcoal dust with the heavy metal ions is easy to separate; the method is simple in operation condition, easy to implement, low in cost and high in removal rate, and does not cause secondary pollution.
Description
Technical field
The invention belongs to environmental pollution improvement field, be specifically related to a kind of method of removing Heavy Metals in Waters ion.
Background technology
Along with the impact of industrial expansion and mankind's activity, the situation of heavy metal contamination becomes increasingly serious.Heavy metal contamination is mainly derived from the heavy metal-containing waste water of the industrial discharges such as metallurgy, process hides, plating, manufacture and organic synthesis.Heavy metal in trade effluent mainly contains lead, zinc, chromium, cadmium, copper, mercury, nickel, cobalt, manganese, vanadium, molybdenum, titanium, antimony, bismuth etc., especially the toxicity of lead, zinc, chromium, cadmium, copper is larger, they can cause by atmosphere, water, food the severe contamination of environment, and can to pass through the approach such as respiratory tract, digestive tube and skin be human intake and accumulation.Such as pollution of chromium, the common valence state of chromium has trivalent and sexavalence.Research shows, trivalent chromium (Cr
3+) be the necessary trace element of human body, sexavalent chrome (Cr
6+) there is strong toxicity, the energy loss DNA of body and animal that hurts sb.'s feelings, and be easily absorbed by the body and accumulate in vivo, be one of confirmed carcinogens.Because chromium produces greatly impact to animals and plants and HUMAN HEALTH, be put into water environment in China priority pollutant Black List, and implemented priority monitoring and management in China.
Both at home and abroad the treatment process of heavy metal wastewater thereby is mainly contained at present: chemical reduction method, electrolytic process, membrane separation process, absorption method, ion exchange method, biological process etc.Wherein absorption method technique is simple, cost is lower, is particularly suitable for lower concentration processing such as chrome waste water containing heavy metal ion.Charcoal has very strong adsorptive power, and raw material sources are wide, fire the features such as convenient and simple, facility investment is few, are desirable sorbing materials.When but charcoal is used for water treatment, its loading capacity is subject to being permitted multifactorial impact, except ambient conditions, main relevant with the specific surface area of charcoal, charcoal particle size reduction, specific surface area increases, micropore quantity increases, and adsorptive power strengthens naturally thereupon, but granularity is less, more easily from reactor, run off and along with pending liquid is discharged from, be difficult to reclaim and Reusability by solid-liquid separation method.
Environmental microorganism recovery technique is used widely in the water body field of repairing as a kind of new technique.In heavy metal polluted waste water is processed, the functional group of microorganism cells wall surface participates in the absorption to heavy metal, has unit specific surface area large, and regenerability is strong, efficiency is high, simple to operate, energy consumption is low and the advantage such as economically feasible.For example, simple mould enrichment and Adsorption of Heavy Metal Ions from the aqueous solution effectively, is a kind of generally acknowledged high-performance bio sorbent material.For the advantage in conjunction with wood charcoal adsorption and microorganism reparation, overcome easy loss, the difficult shortcoming separating, conventionally adopt embedding, crosslinked process for fixation both at home and abroad, but the common indispensable carrier of immobilization operation, embedding medium, linking agent, and immobilization step complexity, need to consume a large amount of chemical reagent.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provides a kind of cost low, the method for environmental protection and segregative removal Heavy Metals in Waters ion.
For solving the problems of the technologies described above, the invention provides a kind of method of removing Heavy Metals in Waters ion, comprise the steps: simple mould spore and heavy metal ion solution to mix, obtain mixing solutions, then in mixing solutions, add wood charcoal powder, cultivate, separating step, complete the absorption to Heavy Metals in Waters ion.
Before simple mould spore and the mixing of heavy metal ion solution, first simple mould spore is made to spore suspension, then join in liquid nutrient medium.Preferably, in spore suspension, the concentration of simple mould spore is 2.0 × 10
6individual/mL.
In aforesaid mixing solutions, the concentration of heavy metal ion is 10～50mg/L.
Aforementioned wood charcoal powder was the wood charcoal powder of 100 mesh sieves.
The addition of aforementioned wood charcoal powder is 1～3g/L, is preferably 2g/L.
Aforementioned culturing step is shaking culture, and temperature is 25～30 DEG C, and rotating speed is 110～150r/min.
Aforementioned separating step is for filtering.
Innovative point of the present invention is: be difficult to simple and easy fixing technical barrier for small particle size charcoal, adopt the method for environmental microorganism recovery technique and the effective combination of wood charcoal adsorption technology to process heavy-metal pollution water body.Traditional carrier is for being immobilized object with microorganism in conjunction with process for fixation, silica gel, gac, wood chip etc. are fixation support, crossover fixation object of the present invention and immobilization carrier, utilize simple mould mycelia for the fixing wood charcoal powder of carrier, realize charcoal and simple mould to sexavalent chrome (Cr in water simultaneously
6+) reduction adsorption effect and to cadmium (Cd
2+), plumbous (Pb
2+), copper (Cu
2+) etc. the adsorption of heavy metal ion, make the charcoal after Adsorption of Heavy Metal Ions be easy to separate, make full use of the absorption property of charcoal.The stability of letter mould is strong, in pending waste water, create growing environment relatively preferably to it, can make its amount reproduction extend mycelia, fully capture the Powdered charcoal in solution, even wood charcoal powder parcel is wound in spherical, and be sunken to liquid bottom and realize solid-liquid layering, simple filtration can easily realize the separation of sorbent material from liquid.
The invention has the beneficial effects as follows:
The method of removal Heavy Metals in Waters ion provided by the invention, operational condition simply and is easily implemented, and cost is lower, and clearance is higher, and heavy metal starting point concentration is below 25mg/L time, sexavalent chrome (Cr
6+), cadmium (Cd
2+), plumbous (Pb
2+) and copper (Cu
2+) clearance all can reach 100%; Wood charcoal powder is sunken to the bottom of liquid simultaneously, and simple filtration just can realize sorbent material and separate from liquid, can not produce secondary pollution, has broad application prospects.
Except object described above, feature and advantage, the present invention also has other object, feature and advantage.Below with reference to figure, the present invention is further detailed explanation.
Brief description of the drawings
The accompanying drawing that forms the application's a part is used to provide a further understanding of the present invention, and schematic description and description of the present invention is used for explaining the present invention, does not form inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 be the embodiment of the present invention 1 containing charcoal pellet form schematic diagram;
Fig. 2 be the embodiment of the present invention 1 containing the microtexture schematic diagram of charcoal bacterium ball under scanning electronic microscope;
Fig. 3 is that the method for the embodiment of the present invention 1 is at different sexavalent chrome (Cr
6+) under starting point concentration to sexavalent chrome (Cr
6+) clearance schematic diagram;
Fig. 4 be the method for the embodiment of the present invention 2 under different wood charcoal powder additions to sexavalent chrome (Cr
6+) clearance schematic diagram;
Fig. 5 is that the method for the embodiment of the present invention 3 is to sexavalent chrome (Cr
6+) clearance temporal evolution schematic diagram.
Embodiment
Below in conjunction with accompanying drawing, embodiments of the invention are elaborated, but the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
Embodiment
In following examples, the material adopting and the instrument of use are commercially available.
Embodiment 1
The simple mould (Penicillium simplicissimum) adopting in the present embodiment, derives from Chinese industrial microbial strains preservation center (China Center of Industrial Culture Collection, CICC), and CICC is numbered 40667.
Sexavalent chrome (Cr in the removal water body of the present embodiment
6+) method, comprise the following steps:
(1) by liquid nutrient medium (aforementioned liquids medium component is as shown in table 1), sexavalent chrome (Cr
6+) solution, wood charcoal powder is sterilizing 20min under 115 DEG C of conditions, then under aseptic condition, is cooled to room temperature.Simple mould spore is placed in to sterilized water and makes spore suspension, in spore suspension, the concentration of simple mould spore is 2.0 × 10
6individual/mL.Aforementioned spore suspension is inoculated in sterilized liquid nutrient medium, has been inoculated liquid nutrient medium.
(2) get 7 groups of above-mentioned liquid nutrient mediums of having inoculated, every group arranges three Duplicate Samples, adds wherein sexavalent chrome (Cr
6+) solution, obtain mixing solutions, make sexavalent chrome (Cr in mixing solutions
6+) concentration is respectively 10mg/L, 20mg/L, 25mg/L, 30mg/L, 35mg/L, 40mg/L, 50mg/L.In mixing solutions, add wood charcoal powder, aforementioned wood charcoal powder is through mechanical disintegration and cross 100 mesh sieves, and wood charcoal powder is 2.0g at every liter containing the addition in chromium liquid nutrient medium.By aforesaid liquid shaking culture, shaking culture temperature is 28 DEG C, and rotating speed is 150r/min, and the shaking culture time is 84h, obtains containing charcoal bacterium ball.
(3) filter after above-mentioned shaking culture containing charcoal bacterium ball, complete sexavalent chrome (Cr in water body
6+) removal.
Be deposited in liquid bottom because mycelia captures wood charcoal powder formation bacterium ball, muddy becomes clarification containing charcoal liquid, containing charcoal pellet form as shown in Figure 1.Filter containing charcoal bacterium ball, after lyophilize, will be placed under scanning electronic microscope containing charcoal bacterium ball, its surface microstructure as shown in Figure 2, the mycelia spreading is wound around charcoal particle, thereby form firm bead, owing to being wound around evenly, retained the most space of charcoal, less on charcoal particle adsorption surface area impact, can ensure preferably the adsorptive power of charcoal.
From each group, get filtrate, measure in the rear liquid of processing and remain sexavalent chrome (Cr
6+) content, measurement result as shown in Figure 3, as shown in Figure 3, sexavalent chrome (Cr
6+) clearance is along with sexavalent chrome (Cr
6+) starting point concentration rising and decline, sexavalent chrome (Cr
6+) starting point concentration is below 25mg/L time, sexavalent chrome (Cr
6+) clearance can reach 100%.
Table 1 liquid culture based component
Embodiment 2
The simple mould (Penicillium simplicissimum) adopting in the present embodiment, derives from Chinese industrial microbial strains preservation center (China Center of Industrial Culture Collection, CICC), and CICC is numbered 40667.
Sexavalent chrome (Cr in a kind of removal water body
6+) method, comprise the following steps:
(1) by liquid nutrient medium (its composition is in table 1), sexavalent chrome (Cr
6+) solution, wood charcoal powder sterilizing 20min under 115 DEG C of conditions, then under aseptic condition, be cooled to room temperature.Simple mould spore is placed in to sterilized water and makes spore suspension, in spore suspension, the concentration of simple mould spore is 2.0 × 10
6individual/mL.Aforementioned spore suspension is inoculated in sterilized liquid nutrient medium, has been inoculated liquid nutrient medium.In liquid nutrient medium, add sexavalent chrome (Cr to above-mentioned inoculation
6+) solution, obtain mixing solutions, make sexavalent chrome (Cr in mixing solutions
6+) concentration is 30mg/L.
(2) get 5 groups of above-mentioned mixing solutionss, every group arranges three Duplicate Samples, in mixing solutions, add respectively wood charcoal powder, wood charcoal powder is through mechanical disintegration and cross 100 mesh sieves, obtain containing charcoal substratum, make the aforementioned content containing wood charcoal powder in charcoal substratum be respectively 1.0g/L, 1.5g/L, 2.0g/L, 2.5g/L, 3.0g/L.By the aforementioned charcoal substratum shaking culture that contains, shaking culture temperature is 28 DEG C, and rotating speed is 150r/min, and the shaking culture time is 84h, obtains containing charcoal bacterium ball.
(3) filter after above-mentioned shaking culture containing charcoal bacterium ball, complete sexavalent chrome (Cr in water
6+) removal.
From each group, get filtrate, measure in the rear liquid of processing and remain sexavalent chrome (Cr
6+) content, measurement result as shown in Figure 4, as shown in Figure 4, along with the increase of wood charcoal powder addition, sexavalent chrome (Cr
6+) clearance is in rising trend, but in the time that wood charcoal powder addition is increased to 3.0g/L from 2.0g/L, sexavalent chrome (Cr
6+) clearance not do not increase pari passu, in addition, after wood charcoal powder addition exceedes 2.0g/L, in solution, all occur that wood charcoal powder is residual, unnecessary wood charcoal powder can not be captured and collect by mycelium pellet, so, mixed economy factor and effect, choose the optimum amount of 2.0g/L as wood charcoal powder.
Embodiment 3
The simple mould (Penicillium simplicissimum) adopting in the present embodiment, derives from Chinese industrial microbial strains preservation center (China Center of Industrial Culture Collection, CICC), and CICC is numbered 40667.
Sexavalent chrome (Cr in a kind of removal water body
6+) method, comprise the following steps:
(1) by liquid nutrient medium (its composition is in table 1), sexavalent chrome (Cr
6+) solution, wood charcoal powder sterilizing 20min under 115 DEG C of conditions, then under aseptic condition, be cooled to room temperature.Simple mould spore is placed in to sterilized water and makes spore suspension, in spore suspension, the concentration of simple mould spore is 2.0 × 10
6individual/mL.Aforementioned spore suspension is inoculated in sterilized liquid nutrient medium, has been inoculated liquid nutrient medium.
(2) in liquid nutrient medium, add sexavalent chrome (Cr to above-mentioned inoculation
6+) solution, make sexavalent chrome (Cr in substratum
6+) concentration is 25mg/L, obtains mixing solutions.In aforementioned mixing solutions, add wood charcoal powder, wood charcoal powder is through mechanical disintegration and cross 100 mesh sieves, and in every liter of mixing solutions, the addition of wood charcoal powder is 2.0g.By above-mentioned mixing solutions shaking culture of having added wood charcoal powder, shaking culture temperature is 28 DEG C, and rotating speed is 150r/min.
(3), every sampling in 12 hours, measure in the rear liquid of processing and remain sexavalent chrome (Cr
6+) content, measurement result as shown in Figure 5, as shown in Figure 5, along with cultivating the increase in reaction times, sexavalent chrome (Cr
6+) removal take the lead in rising trendly, tend towards stability after reaching maximum value, this explanation charcoal is first brought into play and is removed sexavalent chrome (Cr
6+) effect, simple mould spend growth adjustment period progressively adapt to the environment of Cr-containing medium, along with the growth of biomass completes sexavalent chrome (Cr
6+) removal.
Embodiment 4
The simple mould (Penicillium simplicissimum) adopting in the present embodiment, derives from Chinese industrial microbial strains preservation center (China Center of Industrial Culture Collection, CICC), and CICC is numbered 40667.
The removal Heavy Metals in Waters cadmium (Cd of the present embodiment
2+), plumbous (Pb
2+) or copper (Cu
2+) method, comprise the following steps:
(1) by liquid nutrient medium (its composition is in table 1), cadmium (Cd
2+) solution, lead (Pb
2+) solution, copper (Cu
2+) solution, wood charcoal powder sterilizing 20min under 115 DEG C of conditions, then under aseptic condition, be cooled to room temperature.Simple mould spore is placed in to sterilized water and makes spore suspension, in spore suspension, the concentration of simple mould spore is 2.0 × 10
6individual/mL.Aforementioned spore suspension is inoculated in sterilized liquid nutrient medium, has been inoculated liquid nutrient medium.
(2) get three groups of above-mentioned liquid nutrient mediums of having inoculated, every group arranges three Duplicate Samples, and one group is added cadmium (Cd
2+) solution, one group is added plumbous (Pb
2+) solution, one group is added copper (Cu
2+) solution, obtain 3 groups of mixing solutionss.In three groups of aforementioned mixing solutionss, add wood charcoal powder, wood charcoal powder is through mechanical disintegration and cross 100 mesh sieves, and in every liter of mixing solutions, the addition of wood charcoal powder is 2.0g.By aforesaid liquid shaking culture, shaking culture temperature is 28 DEG C, and rotating speed is 150r/min, and the shaking culture time is 84h, obtains containing charcoal bacterium ball.
(3) filter after above-mentioned shaking culture containing charcoal bacterium ball, complete Cadmium In The Water Body (Cd
2+), plumbous (Pb
2+) or copper (Cu
2+) removal.
From each group, get filtrate, measure and process residual gravity metal ion content in rear liquid, result demonstration, when starting weight concentration of metal ions is 30mg/L originally, cadmium (Cd
2+) clearance reaches 94.4%, plumbous (Pb
2+) clearance reaches 95.6%, copper (Cu
2+) clearance reaches 92.1%; When starting weight concentration of metal ions is 25mg/L originally, cadmium (Cd
2+), plumbous (Pb
2+) and copper (Cu
2+) clearance all can reach 100%.
In embodiment 1 to 4, the temperature of shaking culture is 25 DEG C～30 DEG C, and rotating speed is that 110r/min～150r/min all can obtain containing charcoal bacterium ball.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, to those skilled in the art, the present invention can have various modifications and variations.Within every the spirit and principles in the present invention, any amendment of doing, be equal to replacement, improvement etc., within protection scope of the present invention all should be included in.
Claims (8)
1. a method of removing Heavy Metals in Waters ion, is characterized in that, comprises the steps, simple mould spore and heavy metal ion solution are mixed, and obtains mixing solutions; In described mixing solutions, add wood charcoal powder, cultivate, separating step, complete the absorption to Heavy Metals in Waters ion.
2. the method for removal Heavy Metals in Waters ion according to claim 1, is characterized in that, described simple mould spore and heavy metal ion solution are first made spore suspension by simple mould spore before mixing, and then join in liquid nutrient medium.
3. the method for removal Heavy Metals in Waters ion according to claim 2, is characterized in that, the concentration of simple mould spore described in described spore suspension is 2.0 × 10
6individual/mL.
4. according to the method for the removal Heavy Metals in Waters ion described in any one in claims 1 to 3, it is characterized in that, in described mixing solutions, the concentration of heavy metal ion is 10～50mg/L.
5. according to the method for the removal Heavy Metals in Waters ion described in any one in claims 1 to 3, it is characterized in that, described wood charcoal powder is crossed 100 mesh sieves.
6. according to the method for the removal Heavy Metals in Waters ion described in any one in claims 1 to 3, it is characterized in that, the addition of described wood charcoal powder is 1～3g/L.
7. according to the method for the removal Heavy Metals in Waters ion described in any one in claims 1 to 3, it is characterized in that, described culturing step is at 25～30 DEG C of temperature, carries out shaking culture with the rotating speed of 110～150r/min.
8. according to the method for the removal Heavy Metals in Waters ion described in any one in claims 1 to 3, it is characterized in that, described separating step is for filtering.
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| CN105647539A (en) * | 2016-01-28 | 2016-06-08 | 中南大学 | Application of lead-contaminated soil restoring fixing agent synthesized based on microorganism assembly |
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| CN105733599A (en) * | 2016-01-28 | 2016-07-06 | 中南大学 | Cadmium-contaminated soil remediation fixing agent based on microorganism assembly synthesis as well as preparation and application method thereof |
| CN106190871A (en) * | 2016-09-18 | 2016-12-07 | 南京农业大学 | A kind of method that compound thread fungal organism drip leaching with straw as carbon source processes heavy-metal contaminated soil |
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| CN104556399B (en) * | 2014-11-14 | 2016-06-08 | 山东省农业科学院农产品研究所 | A kind of method of purification of heavy metal ion |
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| CN104528930A (en) * | 2015-01-08 | 2015-04-22 | 太原工业学院 | Method for degrading organic chromium in dirt water through microorganism immobilization method |
| WO2017109521A1 (en) | 2015-12-21 | 2017-06-29 | Aristotle University Of Thessaloniki - E.L.K.E. | A method for the synthesis of a bivalent tin oxy-hydroxide adsorbent for the removal of hexavalent chromium from water, particularly drinking water, the adsorbent and its use |
| CN105733599A (en) * | 2016-01-28 | 2016-07-06 | 中南大学 | Cadmium-contaminated soil remediation fixing agent based on microorganism assembly synthesis as well as preparation and application method thereof |
| CN105689374A (en) * | 2016-01-28 | 2016-06-22 | 中南大学 | Application of phosphorus base charcoal material to remediation of lead contaminated soil |
| CN105647539A (en) * | 2016-01-28 | 2016-06-08 | 中南大学 | Application of lead-contaminated soil restoring fixing agent synthesized based on microorganism assembly |
| CN105598158A (en) * | 2016-01-28 | 2016-05-25 | 中南大学 | Phosphorus-based biochar material, and preparation and application thereof |
| CN105733599B (en) * | 2016-01-28 | 2019-04-23 | 中南大学 | A kind of cadmium pollution soil reparation fixative and its methods for making and using same based on microorganism assembling synthesis |
| CN106190871A (en) * | 2016-09-18 | 2016-12-07 | 南京农业大学 | A kind of method that compound thread fungal organism drip leaching with straw as carbon source processes heavy-metal contaminated soil |
| CN106190871B (en) * | 2016-09-18 | 2021-11-30 | 南京农业大学 | Method for treating heavy metal contaminated soil by bioleaching with composite filamentous fungi by taking straws as carbon source |
| CN108841815A (en) * | 2018-06-26 | 2018-11-20 | 常州市蒽盗钟情生物科技有限公司 | A kind of preparation method of the fixed material of microorganism |
| CN113149230A (en) * | 2021-02-26 | 2021-07-23 | 中南大学 | Treatment method for reducing hexavalent chromium by wood charcoal electron transfer enhanced microorganisms |
| CN113149230B (en) * | 2021-02-26 | 2022-04-19 | 中南大学 | Treatment method for reducing hexavalent chromium by wood charcoal electron transfer enhanced microorganisms |
| CN113862163A (en) * | 2021-11-11 | 2021-12-31 | 安徽马钢矿业资源集团南山矿业有限公司 | Penicillium and microbial inoculum with heavy metal ion removal effect and application thereof |
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| CN103910437B (en) | 2015-07-15 |
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